Polymer polysulfides containing ether groups



Patented Aug. 3, 1954 POLYMER POLYSULFIDES CONTAINING ETHER GROUPS FrankK. Signaigo, Kenmore, N. Y., assignor, by mesne assignments, to theUnited States of America as represented by the Secretary of the Na y NoDrawing. Original application December 11,

1945, Serial 2,586,182, dated February 19, 1952.

No. 634,394, now Patent No.

Divided and this application February 1, 1052, Serial 3 Claims.

1 This application is a division of application Serial Number 634,394,filed December 11, 1945, for Polymeric Compounds.

My invention relates to a new class of products and methods whereby theymay be produced.

More particularly, it relates to polyalkylene polysulfides havinglateral ether groups and methods whereby they may be prepared.

In my copending application Serial Number 470,909 of December 31, 1942,now abandoned,

polymeric ethylene polysulfides and a method whereby they may beprepared is disclosed. These compounds are useful for the preparation ofcoatings, impregnations, cementing materials, and the like. They arealso valuable as oil resistant rubber-like materials suitable for themanufacture of oil resistant hose. I have discovered that compoundshaving particular usefulness for the above mentioned purposes and whichare suitable for convenient preparation are obtained when the polymericethylene polysulfides contain lateral ether groups.

The polyalkylene polysulfides having lateral ether groups ascontemplated in this invention have recurring structural units of theformula:

(CHzC|lHS,,-) R

where n is a small integer greater than 1, R a radical containing anether group, and x is the number of recurring structural units in thepolymer.

In accordance with another aspect of my invention the preparation ofpolyalkylene polysulfides having lateral ether groups is obtained byreaction of alkali metal polysulflde with a dihalogenoalkyl ether, asillustrated by the equations The preparation of my new class of productsmay be illustrated by the following examples:

Example 1.--A mixture of 252 parts (1 mol+ of sodium sulfide(Na2S.9HzO-), 68 parts (2 mols+5%) of sulphur, and 90 parts of water isis stirred at 50 C. until all the sulphur is dissolved. To formmagnesium hydroxide, which acts as a dispersing agent in the subsequentpolymer formation, 12 parts of sodium hydroxide are added, followed bythe gradual addition with stirring of a solution of 30.6 parts ofmagnesium chloride (MgClzfiHzO) in parts of water. To the solution ofsodium polysulfide maintained at about C. is then added with stirring,over a period of 3 to 4 hours, 246 parts (1 mol) of 2,3- dibromopropylethyl ether (prepared by bromi hating allyl ethyl ether in chloroform).The polymeric sulfide which separates is digested by stirring thereaction mixture at '10-'75 C. for '7 to 8 hours. After cooling, thecontents of the reaction vessel are poured into a large volume of water,and the solid is washed with water by decantation until the supernatantlayer becomes pale yellow, then air-dried.

Example 2.-A mixture of 252 parts of sodium sulfide (NazELQHzO) 68 partsof sulfur, and 90 parts of water is stirred at 50 C. until all thesulfur is dissolved. 16 parts of sodium hydroxide are added, followed bythe gradual addition with stirring of 41 parts of magnesium chloride(MgClzfil-izo). To the solution of sodium polysulfide maintained atabout 50 C. are then added with stirring, over a period of about 5hours, 232 parts of 2,3-dibromopropyl methyl ether (pre pared bybrcminating allyl methyl ether in chloroform). The resulting polymericsulfide which separates is digested by stirring the reaction mixture at70-75 C. for about 9 hours. After cooling, the polymeric sulfide isfiltered from the reaction mixture, washed cnce with a mixture of equalparts of water and ethyl alcohol, and dried at reduced pressure in adesiccator at room temperature, 193 parts of polymeric product beingobtained.

Example 3.--A solution of sodium polysulfide containing magnesiumhydroxide is prepared in the manner described in the preceding examplefrom 134 parts of sodium sulfide (Na2S.9I-I2O), 35 parts of sulfur, 50parts of water, 8 parts of sodium hydroxide, and 21 parts of magnesiumchloride hexahydrate. To this solution, maintained at about 50 0., areadded with stirring over a period of 2 hours, 132 parts of2,3-dibromopropyl isopropyl ether (prepared by brominating allylisopropyl ether in chloroform). The polymeric sulfide which separates isdigested by stirrinfl the reaction mixture for about 7 hours at 70-'75C. After cooling, the contents of the reaction vessel are poured intowater, the solid washed with water and air dried.

Earample 4.-A mixture of 264 parts of sodium sufide (NazS.9I-iz0) and 71parts of sulfur is melted together by stirring at 50 C. To this solutionof of sodium polysulfide, maintained at about 50 0., is added dropwisewith stirring, over a period of 5 hours, a solution i0 274 parts of2,3-dibromopropy1 n-butyl ether (prepared by prominating allyl n-butylether in chloroform) in 198 parts of methanol. The reaction mixture isthen stirred at 70-75 C. for an additional 18 hours to complete theformation of the polymer. After standing at room temperature for about16 hours, the polymeric sulfide separates from the reaction mixture as aclear taffy-like material. It is Washed by trituration with water andthen with methanol, and is finally dried in a desiccator at reducedpressure.

The above described processes are only by of illustration. The polymericalkoxyethylene polysulfides derived from the methyl, isopropyl, andn-butyl ethers of 2,3-dibromopropanoi can be prepared by the process ofthe above examples. Polysulfides containing aromatic, alkyl-aromatic,cycloaliphatic or heterocyclic ether groups may also be prepared bygenerally similar processes from dihalogenoalkyl ethers having suchgroups attached to the ether oxygen atom.

My new polymeric alkyl ne polysulfides having lateral ether groups areviscous resins, insoluble in Water but soluble in some organic solvents,as for example dioxane. They may be used as intermediates in thepreparation or" vicinal dimercapto ethers by catalytic hydrogenation inthe presence of a sulf-aetive catalyst, such as oobalt sulfide. Thepreparation of such monomeric others is disclosed by A. A. Pavlic and W.J. Peppel in application Ser. No. 568,964, filed December 13, 1944, nowPatent No. 2,397,698, issued April 2, 1946.

My invention is capable of Wide variations from the form described, itsscope being defined in the appended claims.

What is claimed is:

1. The process of preparing a polymeric (ethoxymethyl) ethylenepolysulfide characterized by the reaction: BroH2-oHBroH3ooiH +Na2s,.(CHz-CHS,.),,

HzOCzHs where n is a small integer greater than 1 and :1: is an integergreater than 1.

2. The process of preparing a polymeric (ethoxymethyl) ethylenepolysulfide characterized by the steps of mixing sodium sulfide, sulfur,and water in approximately the following proportions:

Parts Sodium sulfide (Na2S.9H2O) 252 Sulfur 68 Water 90 where n is asmall integer greater than 1 and a: is an integer greater than 1.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,195,380 Patrick Mar. 26, 1940 FOREIGN PATENTS Number CountryDate 385,980 Great Britain Jan. 2, 1933 446,173 Great Britain Apr. 20,1936

3. AS A NEW PRODUCT, A POLYMERIC ETHYLENE POLYSULFIDE HAVING RECURRINGSTRUCTURAL UNITS OF THE FORMULA: